Chalcogenide Devices Exhibiting Stable Operation from the As-Fabricated State

ABSTRACT

A chalcogenide material and chalcogenide memory device having less stringent requirements for formation, improved thermal stability and/or faster operation. The chalcogenide materials include materials comprising Ge, Sb and Te in which the Ge and/or Te content is lean relative to the commonly used Ge 2 Sb 2 Te 5  chalcogenide composition. Electrical devices containing the instant chalcogenide materials show a rapid convergence of the set resistance during cycles of setting and resetting the device from its as-fabricated state, thus leading to a reduced or eliminated need to subject the device to post-fabrication electrical formation prior to end-use operation. Improved thermal stability is manifested in terms of prolonged stability of the resistance of the device at elevated temperatures, which leads to an inhibition of thermally induced setting of the reset state in the device. Significant improvements in the 10 year data retention temperature are demonstrated. Faster device operation is achieved through an increased speed of crystallization, which acts to shorten the time required to transform the chalcogenide material from its reset state to its set state in an electrical memory device.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/975,615, filed on Oct. 17, 2007, which is a continuation of U.S.patent application Ser. No. 11/200,466, filed on Aug. 9, 2005, nowabandoned, the disclosures of which in their entirety are incorporatedby reference herein.

FIELD OF INVENTION

This invention pertains to chalcogenide materials having applications aselectrical and optical memories and switches. More particularly, thisinvention relates to chalcogenide materials showing high reproducibilityof electrical resistance upon transformation from a primarily amorphousstate to a primarily crystalline state on repeated cycles and tochalcogenide materials exhibiting high thermal stability. Mostspecifically, this invention is concerned with off-tieline chalcogenidealloys in the Ge—Sb—Te family having a low Ge concentration.

BACKGROUND OF THE INVENTION

Chalcogenide materials are an emerging class of commercial electronicmaterials that exhibit switching, memory, logic, and processingfunctionality. The basic principles of chalcogenide materials weredeveloped by S. R. Ovshinsky in the 1960's and much effort by him andothers around the world since then have led to advancements of theunderlying science and an expansion of the field of application ofchalcogenide materials.

Early work in chalcogenide devices demonstrated electrical switchingbehavior in which switching from a resistive state to a conductive statewas induced upon application of a voltage at or above the thresholdvoltage of the active chalcogenide material. This effect is the basis ofthe Ovonic Threshold Switch (OTS) and remains an important practicalfeature of chalcogenide materials. The OTS provides highly reproducibleswitching at ultrafast switching speeds for over 10¹³ cycles. Basicprinciples and operational features of the OTS are presented, forexample, in U.S. Pat. Nos. 3,271,591; 5,543,737; 5,694,146; and5,757,446; the disclosures of which are hereby incorporated byreference, as well as in several journal articles including “ReversibleElectrical Switching Phenomena in Disordered Structures”, PhysicalReview Letters, vol. 21, p. 1450-1453 (1969) by S. R. Ovshinsky;“Amorphous Semiconductors for Switching, Memory, and ImagingApplications”, IEEE Transactions on Electron Devices, vol. ED-20, p.91-105 (1973) by S. R. Ovshinsky and H. Fritzsche; the disclosures ofwhich are hereby incorporated by reference.

Another important application of chalcogenide materials is in electricaland optical memory devices. One type of chalcogenide memory deviceutilizes the wide range of resistance values available for the materialas the basis of memory operation. Each resistance value corresponds to adistinct structural state of the chalcogenide material and one or moreof the states can be selected and used to define operational memorystates. Chalcogenide materials exhibit a crystalline state or phase aswell as an amorphous state or phase. Different structural states of achalcogenide material differ with respect to the relative proportions ofcrystalline and amorphous phase in a given volume or region ofchalcogenide material. The range of resistance values is bounded by aset state and a reset state of the chalcogenide material. The set stateis a low resistance structural state whose electrical properties areprimarily controlled by the crystalline portion of the chalcogenidematerial and the reset state is a high resistance structural state whoseelectrical properties are primarily controlled by the amorphous portionof the chalcogenide material.

Each memory state of a chalcogenide memory material corresponds to adistinct resistance value and each memory resistance value signifiesunique informational content. Operationally, the chalcogenide materialcan be programmed into a particular memory state by providing anelectric current pulse of appropriate amplitude and duration totransform the chalcogenide material into the structural state having thedesired resistance. By controlling the amount of energy provided to achalcogenide material, it is possible to control the relativeproportions of crystalline and amorphous phase regions within a volumeof the material and to thereby control the structural (and memory) stateof the chalcogenide material.

Each memory state can be programmed by providing the current pulsecharacteristic of the state and each state can be identified or read ina non-destructive fashion by measuring the resistance. Programming amongthe different states is fully reversible and the memory devices can bewritten and read over a virtually unlimited number of cycles to providerobust and reliable operation. The variable resistance memoryfunctionality of chalcogenide materials is currently being exploited inthe OUM (Ovonic Universal (or Unified) Memory) devices that arebeginning to appear on the market. Basic principles and operation of OUMtype devices are presented, for example, in U.S. Pat. Nos. 6,859,390;6,774,387; 6,687,153; and 6,314,014; the disclosures of which areincorporated by reference herein as well as in several journal articlesincluding “Low Field Amorphous State Resistance and Threshold VoltageDrift in Chalcogenide Materials”, published in IEEE Transactions onElectron Devices, vol. 51, p. 714-719 (2004) by Pirovana et al.; and“Morphing Memory” published in IEEE Spectrum, vol. 167, p. 363-364(2005) by Weiss.

The behavior (including switching, memory, and accumulation) andchemical compositions of chalcogenide materials included within thescope of this invention have been described, for example, in thefollowing U.S. Pat. Nos. 6,671,710; 6,714,954; 6,087,674; 5,166,758;5,296,716; 5,536,947; 5,596,522; 5,825,046; 5,687,112; 5,912,839; and3,530,441, the disclosures of which are hereby incorporated byreference. These references also describe proposed mechanisms thatgovern the behavior of the chalcogenide materials. The references alsodescribe the structural transformations from the crystalline state tothe amorphous state (and vice versa) via a series of partiallycrystalline states in which the relative proportions of crystalline andamorphous regions vary underlying the operation of electrical andoptical chalcogenide materials.

Current commercial development of the chalcogenide materials and devicesis also oriented toward the fabrication of arrays of devices.Chalcogenide materials offer the promise of high density memory, logicand neural arrays that can operate according to traditional binary datastorage or according to a multilevel scheme. Chalcogenide arrays furtheroffer the prospect of integrating, on a single chip, both memory andprocessing capabilities, thereby enabling high speed operation.

In order to further expand the commercial prospects of chalcogenidephase change memories, it is necessary to consider improvements in boththe chemical and physical properties of chalcogenide materials and inmanufacturing processes. A current issue in terms of the properties ofchalcogenide materials is the need to improve the thermal stability ofthe materials. Data in a chalcogenide material are retained as astructural state of the material, so any tendency of the structuralstate to transform with temperature represents a potential undesirablemechanism of erasing or losing data. Many chalcogenide memory materialsretain their structural states for long periods of time at roomtemperature, but become susceptible to variations in the structuralstate upon increasing temperature. In practical terms, this limits thetemperature environment in which chalcogenide memory devices can beutilized as well as the temperatures that can be employed in processingor manufacturing.

In most currently envisioned memory applications, chalcogenide materialsare operated in a binary mode where the memory states correspond to, orapproximately correspond to, the set state and the reset state sincethese states provide the greatest contrast in resistance and thusfacilitate discrimination of the state of the material during read out.In most of the fabrication processes contemplated for commercialproduction of chalcogenide memory devices, the chalcogenide material isdeposited on a substrate, electrical contact layer or other layer in anamorphous or otherwise disordered state and converted to a crystallinestate during subsequent processing. In completed, fully fabricateddevices, it is sometimes necessary to electrically form the chalcogenidematerial in a formation step to ready it for consistent operation as theactive material of a memory element. The formation process includes thestep of transforming the as-processed chalcogenide device to the optimumstate for product use. In order to increase the efficiency ofmanufacturing, it is desirable to transform the chalcogenide material tothe optimum state in a minimal number of pulses and have it ready foroperation by the end-user. In practice, however, formation of thechalcogenide materials in current use requires many cycles of settingand resetting until the resistance of the set state stabilizes to areproducible value.

SUMMARY OF THE INVENTION

The instant invention provides a chalcogenide alloy composition that,when used in electrical chalcogenide memory applications, provides forgreater thermal stability and/or reduced need for or elimination ofpost-fabrication formation electrical stimulus and/or faster operationthrough shorter time-to-set characteristics.

The instant chalcogenide material includes Ge and Sb where the atomicconcentration of Ge is less than or equal to 20% and the atomicconcentration of Sb is greater than or equal to 30%. In a preferredembodiment, the atomic concentration of Ge is less than or equal to 16%and the atomic concentration of Sb is greater than or equal to 40%. Inanother preferred embodiment, the atomic concentration of Ge is lessthan or equal to 12% and the atomic concentration of Sb is greater thanor equal to 50%.

In other preferred embodiments, instant chalcogenide material includesthe foregoing atomic concentrations of Sb and an atomic concentration ofGe between 11% and 19%, more preferably between 13% and 18% and mostpreferably between 15% and 17%.

In still other preferred embodiments, the instant chalcogenide materialincludes Ge and Sb in the foregoing atomic concentration and furtherincludes Te. In one embodiment, the atomic concentration of Te is lessthan or equal to 50% and more preferably between 20% and 50%. In anotherembodiment, the atomic concentration of Te is less than or equal to 40%and more preferably between 30% and 40%. In another embodiment, theatomic concentration of Te is less than or equal to 30%.

The instant invention includes electrical devices containing the instantchalcogenide materials where the devices include a layer of chalcogenidematerial in electrical communication with two electrical terminals orcontacts. The instant invention further includes arrays of such devices.

In some embodiments, the number of electrical pulses required for theformation of devices that incorporate the instant chalcogenide alloys isreduced or eliminated. In one embodiment, formation of the device in itsas-fabricated (virgin) state requires no more than one step of resettingthe device and one step of setting the device. In a more preferredembodiment, no formation of the device in its as-fabricated (virgin)state is required.

In other embodiments, the set resistance of the device stabilizes in afewer number of cycles of setting and resetting such that the variationin the set resistance from cycle-to-cycle is reduced. In one embodiment,the resistance of the first set state of the device differs from theresistance of the virgin state of the device by less than 50%. In apreferred embodiment, the resistance of the first set state of thedevice differs from the resistance of the virgin state of the device byless than 25%. In another preferred embodiment, the resistance of thesecond set state of the device differs from the resistance of the firstset state of the device by less than 25%. In a more preferredembodiment, the resistance of the first set state of the device differsfrom the resistance of the virgin state of the device by less than 15%.In another more preferred embodiment, the resistance of the second setstate of the device differs from the resistance of the first set stateof the device by less than 15%.

In still other embodiments, the thermal stability of data retention isimproved. In one embodiment, the instant alloy has a thermal stabilitysufficient to provide for 10 year data retention at a temperature of atleast 120° C. In a preferred embodiment, the alloy has a thermalstability sufficient to provide for 10 year data retention at atemperature of at least 130° C. In a more preferred embodiment, thealloy has a thermal stability sufficient to provide for 10 year dataretention at a temperature of at least 140° C.

In yet other embodiments, the speed of device operation is improvedthrough a decrease in the time required to set the device. In oneembodiment, the time required to set a device including as an activelayer a chalcogenide material according to the instant invention is lessthan or equal to 75% of the time required to set the same device whenGe_(22.2)Sb_(22.2)Te_(55.5) is used as the active chalcogenide layer. Ina preferred embodiment, the time required to set a device including asan active layer a chalcogenide material according to the instantinvention is less than or equal to 50% of the time required to set thesame device when Ge_(22.2)Sb_(22.2)Te_(55.5) is used as the activechalcogenide layer. In a more preferred embodiment, the time required toset a device including as an active layer a chalcogenide materialaccording to the instant invention is less than or equal to 30% of thetime required to set the same device when Ge_(22.2)Sb_(22.2)Te_(55.5) isused as the active chalcogenide layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. Schematic depiction of the resistance of a chalcogenide materialas a function of energy or current.

FIG. 2. R-I curve of a device that includes Ge_(37.8)Sb_(17.8)Te_(44.4)(Ge₄Sb₂Te₅) as the active chalcogenide material.

FIG. 3. R-I curve of a device that includes Ge_(22.2)Sb_(22.2)Te_(55.5)(Ge₂Sb₂Te₅) as the active chalcogenide material.

FIG. 4. R-I curve of a device that includes Ge_(17.8)Sb_(37.8)Te_(44.4)(Ge₂Sb₄Te₅) as the active chalcogenide material.

FIG. 5. R-I curve of a device that includes Ge_(11.1)Sb_(61.1)Te_(27.8)(GeSb₆Te₃) as the active chalcogenide material.

FIG. 6. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge_(37.8)Sb_(17.8)Te_(44.4) (Ge₄Sb₂Te₅) as the activechalcogenide material.

FIG. 7. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge₂₅Sb₂₅Te₅₀ (Ge₂Sb₂Te₄) as the active chalcogenidematerial.

FIG. 8. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge_(22.2)Sb_(22.2)Te_(55.5) (Ge₂Sb₂Te₅) as the activechalcogenide material.

FIG. 9. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge_(17.8)Sb_(37.8)Te_(44.4) (Ge₂Sb₄Te₅) as the activechalcogenide material.

FIG. 10. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge_(15.5)Sb_(45.5)Te_(38.9) (Ge₂Sb₅Te₄) as the activechalcogenide material.

FIG. 11. Virgin resistance and set resistance upon cycling of a devicethat that includes Ge_(11.1)Sb_(61.1)Te_(27.8) (GeSb₆Te₃) as the activechalcogenide material.

FIG. 12. Stabilized reset current of devices as a function of the atomicconcentrations of Ge, Sb and Te present in the active chalcogenidematerial.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

The instant invention provides chalcogenide materials having improvedthermal stability and greater consistency of resistance characteristicsduring the conditioning cycles associated with the formation process ofan as-deposited material that is completed prior to actual utilizationof the material in a memory device. Since the underlying bases of theseimprovements are related to the structural characteristics ofchalcogenide materials, it is helpful to review the basic principles ofoperation of chalcogenide materials.

An important feature of the chalcogenide materials in the operation ofchalcogenide memory devices and device arrays is their ability toundergo a phase transformation between or among two or more structuralstates. (The importance of phase transformations in memory applicationshas prompted some people to refer to chalcogenide materials as phasechange materials and they may be referred to herein as such.) Thechalcogenide materials have structural states that include a crystallinestate, one or more partially-crystalline states and an amorphous state.The crystalline state may be a single crystalline state or apolycrystalline state. As used herein, a partially-crystalline staterefers to a structural state of a volume of chalcogenide material thatincludes an amorphous portion and a crystalline portion. Generally, aplurality of partially-crystalline states exists for the phase-changematerial that may be distinguished on the basis of the relativeproportion of the amorphous and crystalline portions. Fractionalcrystallinity is one way to characterize the structural states of achalcogenide phase-change material. The fractional crystallinity of thecrystalline state is 100%, the fractional crystallinity of the amorphousstate is 0%, and the partially-crystalline states have fractionalcrystallinities that vary continuously between 0% (the amorphous limit)and 100% (the crystalline limit). Phase-change chalcogenide materialsare thus able to transform among a plurality of structural states thatvary inclusively between fractional crystallinities of 0% and 100%.

Transformations among the structural states of a chalcogenide materialare induced by providing energy to the chalcogenide material. Energy invarious forms can influence the fractional crystallinity of achalcogenide material and hence induce structural transformations.Suitable forms of energy include electrical energy, thermal energy,optical energy or other forms of energy (e.g. particle-beam energy) thatinduce electrical, thermal or optical effects in a chalcogenide materialor combinations of the foregoing forms of energy. Continuous andreversible variability of the fractional crystallinity is achievable bycontrolling the energy environment of a chalcogenide material. Acrystalline state can be transformed to a partially-crystalline or anamorphous state, a partially-crystalline state can be transformed to acrystalline or amorphous state, and an amorphous state can betransformed to a partially-crystalline or crystalline state throughproper control of the energy environment of a chalcogenide material.Some considerations associated with the use of thermal, electrical andoptical energy to induce structural transformations are presented in thefollowing discussion.

The use of thermal energy to induce structural transformations exploitsthe thermodynamics and kinetics associated with the crystalline toamorphous or amorphous to crystalline phase transitions. An amorphousphase may be formed, for example, from a partially-crystalline orcrystalline state by heating a chalcogenide material above its meltingtemperature and cooling at a rate sufficient to inhibit the formation ofcrystalline phases. A crystalline phase may be formed from an amorphousor partially-crystalline state, for example, by heating a chalcogenidematerial above the crystallization temperature for a sufficient periodof time to effect nucleation and/or growth of crystalline domains. Thecrystallization temperature is below the melting temperature andcorresponds to the minimum temperature at which crystallization mayoccur. The driving force for crystallization is typically thermodynamicin that the free energy of a crystalline or partially-crystalline stateis lower than the free energy of an amorphous state so that the overallenergy of a chalcogenide material decreases as the fractionalcrystallinity increases. Formation (nucleation and growth) of acrystalline state or crystalline domains within a partially-crystallinestate is kinetically enabled, so that heating below the melting pointpromotes crystallization by providing energy that facilitates therearrangements of atoms needed to form a crystalline phase or domain.The fractional crystallinity of a partially-crystalline state can becontrolled by controlling the temperature or time of heating of thepartially-crystalline state or by controlling the temperature or rate ofcooling of an amorphous or partially-crystalline state.

The use of electrical energy to induce structural transformations relieson the application of electrical (current or voltage) pulses to achalcogenide material. The mechanism of electrically induced structuraltransformations may be electronic in nature, possibly with anaccompanying or consequent thermal contribution. By controlling themagnitude and/or duration of electrical pulses applied to a chalcogenidematerial, it is possible to vary continuously the fractionalcrystallinity. The influence of electrical energy on the structure of achalcogenide material is frequently depicted in terms of the variationof the electrical resistance of a chalcogenide material with the amountof electrical energy provided or the magnitude of the current or voltagepulse applied to a chalcogenide material. A representative depiction ofthe electrical resistance (R) of a chalcogenide material as a functionof electrical energy or current pulse magnitude (Energy/Current) ispresented in FIG. 1 herein. FIG. 1 shows the variation of the electricalresistance of a chalcogenide material resulting from electrical energyor current pulses of various magnitude and may generally be referred toas a resistance plot.

The resistance plot includes two characteristic response regimes of achalcogenide material to electrical energy. The regimes areapproximately demarcated with the vertical dashed line 10 shown inFIG. 1. The regime to the left of the line 10 may be referred to as theaccumulating regime of the chalcogenide material. The accumulationregime is distinguished by a nearly constant or gradually varyingelectrical resistance with increasing electrical energy that culminatesin an abrupt decrease in resistance at and beyond a threshold energy.The accumulation regime thus extends, in the direction of increasingenergy, from the leftmost point 20 of the resistance plot, through aplateau region (generally depicted by 30) corresponding to the range ofpoints over which the resistance variation is small or gradual to theset point or state 40 that follows an abrupt decrease in electricalresistance. The plateau 30 may be horizontal or sloping. The left sideof the resistance plot is referred to as the accumulating regime becausethe structural state of the chalcogenide material continuously evolvesas energy is applied, with the fractional crystallinity of thestructural state correlating with the total accumulation of appliedenergy. The leftmost point 20 corresponds to the structural state in theaccumulating regime having the lowest fractional crystallinity and maybe referred to as the reset state. This state may be fully amorphous ormay contain some residual crystalline content. As energy is added, thefractional crystallinity increases, and the chalcogenide materialtransforms in the direction of increasing applied energy among aplurality of partially-crystalline states along the plateau 30. Selectedaccumulation states (structural states in the accumulation region) aremarked with squares in FIG. 1. Upon accumulation of a threshold amountof applied energy, the fractional crystallinity of the chalcogenidematerial increases sufficiently to effect a setting transformationcharacterized by a dramatic decrease in electrical resistance andstabilization of the set state 40. The structural states in theaccumulation regime may be referred to as accumulation states of thechalcogenide material. Structural transformations in the accumulatingregime are unidirectional in the sense that they progress in thedirection of increasing applied energy within the plateau region 30 andare reversible only by first driving the chalcogenide material throughthe set point 40 and resetting. The behavior illustrated in FIG. 1 isreproducible over many cycles of setting and resetting a devicecontaining a chalcogenide material by applying the requisite energy orcurrent. Once the reset state is obtained, lower amplitude currentpulses can be applied and the accumulation response of the chalcogenidematerial can be retraced. It is thus possible to cycle between the setand reset states over multiple cycles, a necessary feature for longmemory cycle life.

While not wishing to be bound by theory, the instant inventors believethat the addition of energy to a chalcogenide material in theaccumulating regime leads to an increase in fractional crystallinitythrough the nucleation of new crystalline domains or growth of existingcrystalline domains or a combination thereof. It is believed that theelectrical resistance varies only gradually along the plateau 30 despitethe increase in fractional crystallinity because the crystalline domainsform or grow in relative isolation of each other so as to prevent theformation of a contiguous crystalline network that spans thechalcogenide material between the two device electrodes. This type ofcrystallization may be referred to as sub-percolation crystallization.The setting transformation coincides with a percolation threshold inwhich a contiguous, interconnected crystalline network forms within thechalcogenide material between the two device electrodes. Such a networkmay form, for example, when crystalline domains increase sufficiently insize to impinge upon neighboring domains. Since the crystalline phase ofchalcogenide materials is more conductive and less resistive than theamorphous phase, the percolation threshold corresponds to the formationof a contiguous low resistance conductive pathway through thechalcogenide material. As a result, the percolation threshold is markedby a dramatic decrease in the resistance of the chalcogenide material.The leftmost point of the accumulation regime may be an amorphous stateor a partially-crystalline state lacking a contiguous crystallinenetwork. Sub-percolation crystallization commences with an initialamorphous or partially-crystalline state and progresses through aplurality of partially-crystalline states having increasingly higherfractional crystallinities until the percolation threshold is reachedand the setting transformation occurs.

The regime to the right of the line 10 of FIG. 1 may be referred to asthe grayscale regime or grayscale region. The grayscale regime extendsfrom the set state 40 through a plurality of intermediate states(generally depicted by 50) to a reset point or state 60. The variouspoints in the grayscale regime may be referred to as grayscale states ofthe chalcogenide material. Selected grayscale states are marked withcircles in FIG. 1. Structural transformations in the grayscale regimemay be induced by applying an electric current or voltage pulse to achalcogenide material. In FIG. 1, an electric current pulse isindicated. In the grayscale regime, the resistance of the chalcogenidematerial varies with the magnitude of the applied electric pulse. Theresistance of a particular state in the grayscale regime ischaracteristic of the structural state of the chalcogenide material, andthe structural state of a chalcogenide material is dictated by themagnitude of the current pulse applied in the grayscale region. Thefractional crystallinity of the chalcogenide material decreases as themagnitude of the current pulse increases. The fractional crystallinityis highest for grayscale states at or near the set point 40 andprogressively decreases as the reset state 60 is approached. Thechalcogenide material transforms from a structural state possessing acontiguous crystalline network at the set state 40 to a structural statethat is amorphous or substantially amorphous or partially-crystallinewithout a contiguous crystalline network at the reset state 60. Theapplication of current pulses having increasing magnitude has the effectof converting portions of the crystalline network into an amorphousphase and ultimately leads to a disruption or interruption of contiguoushigh-conductivity crystalline pathways in the chalcogenide material. Asa result, the resistance of the chalcogenide material increases as themagnitude of an applied current pulse increases in the grayscale region.

In contrast to the accumulating region, structural transformations thatoccur in the grayscale region are reversible, bi-directional, and thisregion may thus also be referred to as the direct overwrite region ofthe resistance plot. As indicated hereinabove, each state in thegrayscale region may be identified by its resistance and a current pulsemagnitude, where application of that current pulse magnitude induceschanges in fractional crystallinity that produce the particularresistance value of the state. Application of a subsequent current pulsemay increase or decrease the fractional crystallinity relative to thefractional crystallinity of the initial state of the chalcogenidematerial. If the subsequent current pulse has a higher magnitude thanthe pulse used to establish the initial state, the fractionalcrystallinity of the chalcogenide material decreases and the structuralstate is transformed from the initial state in the direction of thereset state along the greyscale resistance curve. Similarly, if thesubsequent current pulse has a lower magnitude than the pulse used toestablish the initial state, the fractional crystallinity of thechalcogenide material increases and the structural state is transformedfrom the initial state in the direction of the set state along thegrayscale resistance curve.

In OUM (Ovonic Unified (or Universal) Memory) applications, thegreyscale states of the chalcogenide material are used to define memorystates of a memory device. Most commonly, the memory devices are binarymemory devices that utilize two of the greyscale states as memorystates, where a distinct information value (e.g. “0” or “1”) isassociated with each state. Each memory state thus corresponds to adistinct structural state of the chalcogenide material and readout oridentification of the state can be accomplished by measuring theresistance of the material (or device) since each structural state ischaracterized by a distinct resistance value as exemplified, forexample, by the greyscale states in FIG. 1. The operation oftransforming a chalcogenide material to the structural state associatedwith a particular memory state may be referred to herein as programmingthe chalcogenide material or writing to the chalcogenide material orstoring information in the chalcogenide material.

To facilitate readout and to minimize readout error, it is desirable toselect the memory states of a binary memory device so that the contrastin resistance of the two states is large. Typically the set state (or astate near the set state) and the reset state (or a state near the resetstate) are selected as memory states in a binary memory application. Theresistance contrast depends on details such as the chemical compositionof the chalcogenide, the thickness of the chalcogenide material in thedevice and the geometry of the device. For a layer of phase-changematerial having the composition Ge₂₂Sb₂₂Te₅₆, a thickness of ˜600 Å, andpore diameter of below ˜0.1 μm in a typical two-terminal devicestructure, for example, the resistance of the reset state is ˜100-1000kΩ and the resistance of the set state is under ˜10 kΩ. Phase-changematerials in general show resistances in the range of ˜100 kΩ to ˜1000kΩ in the reset state and resistance of ˜0.5 kΩ to ˜50 kΩ in the setstate. In the preferred phase-change materials, the resistance of thereset state is at least a factor of two, and more typically an order ofmagnitude or more, greater than the resistance of the set state. Inaddition to binary (single bit) memory applications, chalcogenidematerials may be utilized as non-binary or multiple bit memory materialsby selecting three or more states from among the greyscale states andassociating an information value with each state, where each memorystate corresponds to a distinct structural state of the chalcogenide andis characterized by a distinct resistance value.

One embodiment of the instant invention provides chalcogenide materialshaving improved thermal stability. The improved thermal stability ismanifested as a prolongation of the retention of the structural statesassociated with the memory states of the chalcogenide upon increasingtemperature. As described hereinabove, the application of energy,including thermal energy, may lead to an alteration of the structuralstate of a volume of chalcogenide material through a variation in therelative proportions and/or arrangement of crystalline and amorphousphase regions contained within the volume. As the structural statevaries, the resistance of the material changes and no longer correspondsto the value programmed into the material during the storage operation.If the deviation is sufficiently large, it may not be possible todiscern which state the material was programmed into and as a result,the original information stored into the material is lost and the memoryis unreliable. Since reliable operation of chalcogenide memory devicesat elevated temperatures is necessary for many applications, it isdesirable to develop chalcogenide materials that resist structuralmodifications in high temperature environments. Furthermore, in devicefabrication, it is necessary to deposit ancillary layers (e.g. electrodelayers, insulating layers, barrier layers etc.) on top of a chalcogenidelayer and the thermal stability of the chalcogenide imposes limits onthe deposition and other processing conditions associated with providingsuch layers.

Another embodiment of the instant invention provides chalcogenidematerials capable of undergoing more efficient formation of theas-processed material or device. As used herein, as-processed materialand device refer to the state or properties of the chalcogenide materialor the device containing the chalcogenide material following fabricationand prior to any post-fabrication electrical treatment. Formation is apost-fabrication electrical conditioning process that is used to preparean as-processed material or device for use as a memory (or thresholdswitching) material or device.

As indicated hereinabove, typically the set and reset states areselected as the memory states of a binary memory device. In order formemory operation to be reliable, it is necessary for the resistancevalues of the set and reset states to be reproducible over the multiplecycles of setting and resetting associated with the writing (storing),erasing and rewriting of information over the life of the memory device.It is further desirable for the device, in the as-processed state, toexhibit resistance values corresponding to those to be used in actualapplication.

In prior art chalcogenide memory devices, the resistances of the setand/or reset states of the device in the as-processed state frequentlydeviate from the values used in the ultimate application of the device.More specifically, when electrical energy or pulses is used to transformthe device between the set and reset states, the resistances values varyfrom cycle-to-cycle over several cycles until they stabilize to thevalues that will be used in actual operation. The formation process is apost-fabrication electrical stimulus that is used to condition anas-processed device to the state in which it will operate in actualapplication. In the formation process, the as-processed device isconditioned by cycling it through the set and reset states for asufficient number of conditioning cycles to reach stable resistancesvalues for those states.

The instant devices include a chalcogenide alloy that greatlyfacilitates the formation process by reducing the number of conditioningcycles needed to achieve stable values of relevant operating parameterssuch as resistances of memory states (e.g. set state and reset state aswell as other selected memory states if desired) and the thresholdswitching voltage for the reset state. In one embodiment, formation isaccomplished in no more than three conditioning cycles. In a preferredembodiment, formation is accomplished in no more than two conditioningcycles. In a more preferred embodiment, formation is accomplished in nomore than one conditioning cycle. In a most preferred embodiment, noformation is needed and the device as-processed is ready for operation.

The chalcogenide materials used in the instant devices include alloys ofgermanium (Ge), antimony (Sb) and tellurium (Te) where the Ge and/or Teconcentration is lean relative to the conventional Ge₂Sb₂Te₅ compositionof the prior art. While not wishing to be bound by theory, the instantinventors believe that compositions lean in Ge or Te are beneficialbecause they have a tendency to reduce, minimize or potentiallyeliminate oxidation of the chalcogenide material and/or oxidation of theinterface between the chalcogenide material and either or both of thetop and bottom electrodes in the device structure. It is postulated thatGe has a tendency to getter oxygen during device fabrication,potentially incorporating oxygen and/or forming one or more germaniumoxide phases or layers that must be broken down, removed or renderedharmless during the electrical formation process in order to stabilizethe operational characteristics of the device. The presence of agermanium oxide phase or component in the chalcogenide material or at anelectrode interface with the chalcogenide material leads to an increasein the resistance measured between the top and bottom electrodes of theas-formed device since oxide phases are generally resistive. In thisview, the formation is a process in which undesired oxide phases arebroken down or redistributed within the active volume of chalcogenidematerial to provide a more homogenous chalcogenide region and thus moreconsistent and reproducible operation. By decreasing the Geconcentration in the chalcogenide alloy, it is believed that less oxygenmay become incorporated and as a result, that less or no formation orconditioning is needed to ready the as-processed device for practicalapplication.

While not wishing to be bound by theory, the instant inventors furtherhypothesize that other factors may also contribute to or even dominatethe behavior of the instant chalcogenide materials when used as activematerials in an electrical memory device. Compositions that contain ahigh Ge concentration are believed to promote phase segregation of thechalcogenide material during fabrication, annealing and/or deposition.There may be two consequences of the tendency of a chalcogenide materialto phase segregate when the Ge concentration is high. First, theas-fabricated device may include a chalcogenide material that may not behomogeneous, but rather may contain a combination of Ge-rich andSb/Te-rich phases. If so, the formation process may lead to ahomogenization of the phases through melting and recrystallizing toproduce a chalcogenide material that exhibits stable, uniform andreproducible properties.

Second, if processing and fabrication are controlled to permit formationof a uniform chalcogenide material in the as-fabricated device,subsequent operation of the device through cycling between the set andreset states may induce phase segregation to produce a Ge-rich phase anda Ge-lean phase in the chalcogenide layer. Such an effect may occur ifthe chalcogenide composition melts incongruently. During operation ofthe chalcogenide memory device, there may exist a temperature gradientbetween the top and bottom electrodes. In many common device designs,the bottom electrode is believed to become hotter than the topelectrode, resulting in a temperature gradient that provides adifferential melting effect of the volume of chalcogenide material.Material near the bottom electrode may become hotter, melt moreefficiently and show a greater tendency to phase segregate duringoperation. After a certain number of cycles, an equilibrium point may bereached in which an equilibrium amount of Ge is phase segregated. Oncean equilibrium amount of Ge is segregated, it may further be subject toelectromigration (perhaps toward the bottom electrode) in the presenceof the voltages applied during operation of the device. If so, theformation process may correspond to the process of phase segregating ofan equilibrium amount of Ge along with electromigration of thephase-segregated Ge to an equilibrium position within the pore of thedevice. Upon conclusion of formation, the chalcogenide has reached astable, reproducible state.

In one embodiment, the alloy is a Ge—Sb—Te material having a Geconcentration of 11%-19%. In a preferred embodiment, the alloy is aGe—Sb—Te material having a Ge concentration of 13%-18%. In a morepreferred embodiment, the alloy is a Ge—Sb—Te material having a Geconcentration of 15%-17%.

Example 1

In this example, the fabrication of memory devices having activechalcogenide layers in accordance with the instant invention isdescribed. The device structure is a commonly utilized two-terminaldevice design having an active chalcogenide layer in a pore geometry inelectrical contact with top and bottom electrodes. Two different deviceconfigurations were used and similar results were achieved for each.Both designs were deposited on an Si wafer with a thick SiO₂ surfaceoxide layer.

In one design, a tungsten layer was deposited on the surface oxide andanother SiO₂ layer was deposited thereon. A 600 Å diameter opening wasformed in the deposited SiO₂ layer and was filled with TiN. The tungstenlayer and TiN layers serves as a bottom electrode. A chalcogenide layerhaving a thickness of 500 Å was deposited on the TiN filled opening andsurrounding SiO₂ layers. A top electrode was next deposited in situ andincluded a 400 Å carbon layer deposited on top of the chalcogenide layerand one or more conductive layers deposited on top of the carbon layer.The conductive layers typically included a 300 Å TiN layer and a 500 ÅTi layer.

In a second design, a 350 Å bottom electrode layer (e.g. titaniumaluminum nitride) was deposited on the surface oxide layer and aninsulating layer (e.g. SiO₂) was deposited on the bottom electrode. Apore having a diameter of approximately 800 Å was formed in theinsulating layer. A chalcogenide layer having a thickness of 500 Å wasthen deposited. The chalcogenide layer coated the pore and extendedlaterally over the surrounding insulating layer. A top electrode wasnext in situ deposited and included a 400 Å carbon layer deposited ontop of the chalcogenide layer and one or more conductive layersdeposited on top of the carbon layer. The conductive layers typicallyincluded a 300 Å TiN layer and a 500 Å Ti layer.

Appropriate lithography and patterning was performed on each devicedesign to permit addressing of the devices and the devices weresubjected to annealing at 300° C. for 30 minutes. Both device designsare well-known in the art and further information about chalcogenidephase change memory cells can be found in, for example, U.S. Pat. Nos.5,166,758; 5,296,716; 5,414,271; 5,359,205; and 5,534,712; thedisclosures of which are hereby incorporated by reference.

The chalcogenide layer of each memory device of this EXAMPLE wasdeposited at 200° C. using an RF co-sputtering process. Targets ofGe₂Sb₂Te₅, Ge, Sb and Te were used in the deposition. By controlling thepower, ion energetics, time of exposure and utilization of the differenttargets in the sputtering process, chalcogenide films of differentcomposition were prepared. Memory devices having chalcogenide layerswith the following compositions were fabricated:

Chalcogenide Material Ge (at. %) Sb (at. %) Te (at. %) Ge:Sb:Te RatioGe_(0.07)Sb_(0.77)Te_(0.17) 7 77 17 1:10:2 Ge_(0.09)Sb_(0.69)Te_(0.22) 969 22 1:7:2 Ge_(11.1)Sb_(61.1)Te_(27.8) 11.1 61.1 27.8 1:6:3Ge_(13.5)Sb₅₃Te_(33.5) 13.5 53 33.5 3:12:8 Ge_(15.5)Sb_(45.5)Te_(38.9)15.5 45.5 38.9 2:5:4 Ge_(17.8)Sb_(37.8)Te_(44.4) 17.8 37.8 44.4 2:4:5Ge₂₀Sb₃₀Te₅₀ 20.0 30.0 50.0 2:3:5 Ge₂₀Sb₆₅Te₁₅ 20 65 15 4:13:3Ge_(22.2)Sb_(22.2)Te_(55.5) 22.2 22.2 55.5 2:2:5 Ge₂₅Sb₂₅Te₅₀ 25.0 25.050.0 2:2:4 Ge₂₅Sb₄₀Te₃₅ 25.0 40.0 35.0 5:8:7 Ge₂₅Sb₄₅Te₃₀ 25.0 45.0 30.05:9:6 Ge₂₅Sb₅₀Te₂₅ 25.0 50.0 25.0 1:2:1 Ge_(30.5)Sb_(30.5)Te_(38.9) 30.530.5 38.9 4:4:5 Ge₃₁Sb₅₄Te₁₅ 31 54 15 6:11:3 Ge_(36.1)Sb_(36.1)Te_(27.8)36.1 36.1 27.8 4:4:3 Ge_(37.8)Sb_(17.8)Te_(44.4) 37.8 17.8 44.4 4:2:5Ge₄₂Sb₄₃Te₁₅ 42 43 15 3:3:1 Ge_(45.5)Sb_(15.5)Te_(38.9) 45.5 15.5 38.96:2:5 Ge_(61.1)Sb_(11.1)Te_(27.8) 61.1 11.1 27.8 6:1:3where compositions are listed in atomic percentages of the elementsincluded in the chalcogenide layer of each device. The atomicpercentages may also be referred to herein as the atomic concentration.The Ge:Sb:Te ratio is approximate and corresponds to the approximatechemical stoichiometry of the chalcogenide layer. Many devices usingeach of the chalcogenide compositions were fabricated for this example.

Example 2

In this example, the improved formation characteristics of devicesaccording to the instant invention are described. As describedhereinabove, formation is a process that involves the post-fabricationelectrical conditioning of a device to prepare it for its endapplication. Formation is required for the currently availablechalcogenide memory devices and requires a series of electricalconditioning cycles that include setting and resetting the device untilstable resistances are achieved for the set and reset states. In thisexample, we demonstrate the ability of devices using the instantchalcogenide materials to reduce or eliminate the need for formation.The devices used in this example correspond to those described inEXAMPLE 1 hereinabove. Devices included selected chalcogenidecompositions from those presented in EXAMPLE 1 are described.

To evaluate the formation requirements of a device, we measured theresistance of the device in its as-fabricated state and subjected it tomultiple cycles of setting and resetting to assess whether and to whatextent the set state resistance varies on cycling. The resistance of theas-fabricated device was measured after fabrication and before anyattempt to set or reset the device through electrical means was made.The resistance of the as-fabricated device may be referred to herein asthe virgin resistance of the device or, alternatively, as the resistanceof the virgin state of the device. After measurement of the virginresistance, the device was cycled through its set and reset states. Thecycling entailed measurements of the R-I (resistance-current)characteristics of the device using standard procedures. A series ofvoltage pulses was applied between the top and bottom electrodes of thedevice and the device pulse current and post-pulse low voltage (0.4 V)resistance were measured in response to each pulse. The series of pulsesbegan with a 0.2V pulse and continued with pulses with amplitudesincreasing in 0.2V increments up to a maximum pulse voltage of 7V. Thepulse current and resulting low voltage (0.4 V) resistance measured foreach pulse were plotted to form an R-I curve and from the R-I curve, theset resistance and reset resistance of the device were obtained. Theprocess was repeated over several cycles until the set resistancestabilized. R-I measurements were made on four different devices foreach of the chalcogenide compositions measured.

Representative results from the R-I measurements are shown in FIGS. 2-5for devices that include Ge_(37.8)Sb_(17.8)Te_(44.4) (Ge₄Sb₂Te₅),Ge_(22.2)Sb_(22.2)Te_(55.5) (Ge₂Sb₂Te₅), Ge_(17.8)Sb_(37.8)Te_(44.4)(Ge₂Sb₄Te₅) and Ge_(11.1)Sb_(61.1)Te_(27.8) (GeSb₆Te₃), respectively, asthe active chalcogenide material. In each of FIGS. 2-5, the data pointsdepicted as diamonds correspond to the R-I curve that began with thedevice in its as-fabricated state. The leftmost data point of thediamond data set corresponds to the virgin resistance of the device.Voltages of increasing amplitude are subsequently applied as describedhereinabove to produce the other data points in the diamond set. Higherpulse amplitudes correspond to higher currents. The minimum resistanceresulting from application of the voltage pulses corresponds to theresistance of the set state. The diamond data set shows an increase inresistance at the high end of applied pulse amplitudes. As describedhereinabove, the resistance increase marks the transition to the resetstate. Upon reaching the reset state, the measurement is stopped and theexperiment is repeated to cycle once again through the set state andreset state of the device.

FIG. 2 shows a comparison of two cycles of a device including Ge₄Sb₂Te₅as the active material. The cycle beginning with the as-fabricateddevice is the lower set of data points (diamonds) and the other data set(squares) corresponds to the cycle obtained following attainment of thereset state of the as-fabricated device. FIG. 2 shows a markeddifference in the resistance of the set state for the two cycles andthis difference demonstrates the need to form a device based onGe₄Sb₂Te₅.

FIG. 3 shows a comparison of five cycles of a device including Ge₂Sb₂Te₅as the active material. The cycle beginning with the as-fabricateddevice is the lower set of data points (diamonds). The data pointsindicated with squares correspond to the next cycle, which is the cyclethat begins after the as-fabricated device has been once transformed tothe reset state. Data for an additional three cycles are also shown.FIG. 3 indicates that the resistance of the set state varies over thefirst three cycles and then stabilizes. The device including Ge₂Sb₂Te₅thus requires formation before a stable set state resistance is achievedand the data show a significant difference in the set resistanceobserved upon setting the virgin state and the stabilized resistance ofthe set state after formation.

FIG. 4 shows a comparison of three cycles of a device includingGe₂Sb₄Te₅ as the active material. The cycle beginning with theas-fabricated device is the lower set of data points (diamonds). Thedata points indicated with squares correspond to the next cycle, whichis the cycle that begins after the as-fabricated device has been oncetransformed to the reset state. The data points indicated with trianglescorrespond to the next cycle, which is the cycle that begins after theas-fabricated device has been twice transformed to the reset state. Forthis chalcogenide composition, the resistance of the set state variesonly slightly upon cycling and the resistance of the set state obtainedupon setting the virgin state corresponds closely with the resistance ofthe set state obtained in later cycles. The data of FIG. 4 indicate thata device that includes Ge₂Sb₄Te₅ as the active chalcogenide materialrequires essentially no formation and is ready for use in its finallyapplication in the as-fabricated state.

FIG. 5 shows a comparison of four cycles of a device including GeSb₆Te₃as the active material. The cycle beginning with the as-fabricateddevice is the lower set of data points (diamonds). The data pointsindicated with squares correspond to the next cycle, which is the cyclethat begins after the as-fabricated device has been once transformed tothe reset state. The data points indicated with triangles correspond tothe next cycle, which is the cycle that begins after the as-fabricateddevice has been twice transformed to the reset state. The data pointsindicated with crosses correspond to the next cycle, which is the cyclethat begins after the as-fabricated device has been transformed to thereset state three times. For this chalcogenide composition, theresistance of the set state varies only slightly upon cycling and theresistance of the set state obtained upon setting the virgin statecorresponds closely with the resistance of the set state obtained inlater cycles. The data of FIG. 5 indicate that a device that includesGeSb₆Te₃ as the active chalcogenide material requires essentially noformation and is ready for use in its finally application in theas-fabricated state.

The set state resistances of devices including selected of the instantchalcogenide compositions as the active material are summarized in FIGS.6-11. For each of the selected illustrative chalcogenide compositions,the set resistances of four separate devices is illustrated. Commonterminology is used in each of the figures. Rvirgin refers to theresistance of the virgin state of the device and may be referred toherein as the virgin resistance of the device. Rset0 refers to theresistance of the set state obtained upon setting the virgin state ofthe device (without a prior reset) and may be referred to herein as theresistance of the first set state of the device. Rset1 refers to theresistance of the set state obtained after the device has been reset onetime and may be referred to herein as the resistance of the second setstate of the device. Rset2 refers to the resistance of the set stateobtained after the device has been reset two times and may be referredto herein as the resistance of the third set state of the device. Rset3refers to the resistance of the set state obtained after the device hasbeen reset three times and may be referred to herein as the resistanceof the fourth set state of the device. Four results are shown for eachof Rvirgin, Rset0, Rset1, Rset2, and Rset3 in FIGS. 6-11 to indicate theresults for different devices utilizing each of the selectedillustrative chalcogenide materials. The different devices were selectedfrom different portions of the wafer. The data are presented in the formof bar graphs where the bar graphs of the different set states (Rset0,Rset1, Rset2, and Rset3) for a particular device containing each of thechalcogenide materials are depicted in a common greyscale shade. The bargraph shows the resistance of the set state for the four devices overthe initial few cycles of setting and resetting the device. Resistancesof the first set state, second set state, third set state and fourth setstate are shown. The bar graphs illustrate the extent to which devicesbased on each of the selected illustrative chalcogenide materialsrequire formation.

FIG. 6 shows the results for the device that includesGe_(37.8)Sb_(17.8)Te_(44.4) (approximate composition: Ge₄Sb₂Te₅) as theactive chalcogenide material. This material includes 37.8% Ge, 17.8% Sb,and 44.4% Te. The results indicate that the set resistance Rset0 of thevirgin state is lower than the virgin resistance and that the setresistance Rset1 following the first reset is much higher than eitherthe virgin resistance or Rset0. Set resistances Rset2 and Rset3following subsequent set-reset cycles are similar to Rset1 for thedevices. FIG. 6 indicates that stabilization of the set resistance ofthe device requires a formation process that includes at least one stepin which the device is set and at least one step in which the device isreset. An as-fabricated device that includes Ge_(37.8)Sb_(17.8)Te_(44.4)as the active chalcogenide material is not ready for use in its intendedmemory application since the stabilized set resistance deviatessignificantly from the virgin resistance and since conditioning of thedevice is needed to stabilize its performance.

FIG. 7 shows the results for the device that includes Ge₂₅Sb₂₅Te₅₀(Ge₂Sb₂Te₄) as the active chalcogenide material. This material includes25% Ge, 25% Sb, and 50% Te. The results indicate that the step ofsetting the virgin state of the as-fabricated device leads to asignificant reduction in the set resistance as Rset0 is much lower thanRvirgin. A smaller decrease in the set resistance is observed uponsetting following a reset step to achieve Rset1 and subsequent cycles ofreset-set lead to a stabilization of the set resistance. FIG. 7indicates that stabilization of the set resistance of the devicerequires a formation process that includes at least one step in whichthe device is set and at least one step in which the device is reset. Anas-fabricated device that includes Ge₂Sb₂Te₄ as the active chalcogenidematerial is not ready for use in its intended memory application sincethe stabilized set resistance deviates significantly from the virginresistance and since conditioning of the device is necessary in order tostabilize its performance.

FIG. 8 shows the results for the device that includesGe_(22.2)Sb_(22.2)Te_(55.5) (Ge₂Sb₂Te₅) as the active chalcogenidematerial. This material includes 22.2% Ge, 22.2% Sb, and 55.5% Te. Theresults indicate that the step of setting the virgin state of theas-fabricated device leads to a significant reduction in the setresistance as Rset0 is much lower than Rvirgin. An increase in the setresistance is observed upon setting following a reset step to achieveRset1 and subsequent cycles of reset-set lead to a stabilization of theset resistance. FIG. 8 indicates that stabilization of the setresistance of the device requires a formation process that includes atleast one step in which the as-fabricated device is set and at least onestep in which device is reset. Consequently, an as-fabricated devicethat includes Ge₂Sb₂Te₅ as the active chalcogenide material is not readyfor use in its intended memory application since the stabilized setresistance deviates from the virgin resistance and a conditioningprocess that includes at least a set step and a reset step is necessaryto stabilize the performance of the device.

FIG. 9 shows the results for the device that includesGe_(17.8)Sb_(37.8)Te_(44.4) (approximate composition: Ge₂Sb₄Te₅) as theactive chalcogenide material. This material includes 17.8% Ge, 37.8% Sb,and 44.4% Te. The results indicate that the step of setting the virginstate of the as-fabricated device leads to only a slight reduction inthe set resistance as Rset0 is only slightly lower than Rvirgin.Subsequent cycles of reset-set show that Rset1 is similar to Rset0 andonly slightly lower than Rvirgin. FIG. 9 indicates that stabilization ofthe set resistance of the device is nearly accomplished in theas-fabricated device and that a formation process is either not requiredor requires only the step of setting the device. Consequently, anas-fabricated device that includes Ge_(17.8)Sb_(37.8)Te_(44.4) as theactive chalcogenide material is ready or nearly ready for use in itsintended memory application since the stabilized set resistance issimilar to or deviates only slightly from the virgin resistance andlittle or no conditioning is necessary to stabilize the performance ofthe device.

FIG. 10 shows the results for the device that includesGe_(15.5)Sb_(45.5)Te_(38.9) (approximate composition: Ge₂Sb₅Te₄) as theactive chalcogenide material. This material includes 15.5% Ge, 45.5% Sb,and 38.9% Te. The results indicate that the step of setting the virginstate of the as-fabricated device leads to only a minimal reduction inthe set resistance as Rset0 is very nearly the same as Rvirgin.Subsequent cycles of reset-set show that Rset1, Rset2, and Rset3 aresimilar to Rset0 and also only minimally different from Rvirgin. FIG. 10indicates that stabilization of the set resistance of the device isaccomplished or nearly accomplished in the as-fabricated device and thata formation process is essentially not required. Consequently, anas-fabricated device that includes Ge_(15.5)Sb_(45.5)Te_(38.9) as theactive chalcogenide material is basically ready for use in its intendedmemory application without conditioning or formation since thestabilized set resistance is very nearly the same as the virginresistance.

FIG. 11 shows the results for the device that includesGe_(11.1)Sb_(61.1)Te_(27.8) (approximate composition: Ge₁Sb₆Te₃) as theactive chalcogenide material. This material includes 11.1% Ge, 61.1% Sb,and 27.8% Te. The results indicate that the step of setting the virginstate of the as-fabricated device leads to essentially no change in theset resistance as Rset0 is essentially the same as Rvirgin. Subsequentcycles of reset-set show that Rset1, Rset2, and Rset3 are alsoessentially the same as Rvirgin. FIG. 11 indicates that stabilization ofthe set resistance of the device is essentially accomplished in theas-fabricated device and that no formation process is required.Consequently, an as-fabricated device that includesGe_(11.1)Sb_(61.1)Te_(27.8) as the active chalcogenide material is readyfor use in its intended memory application since the stabilized setresistance is similar to or deviates only slightly from the virginresistance and little or no conditioning is necessary to stabilize theperformance of the device.

The results of this example demonstrate that the number of stepsrequired for the formation of devices that incorporate the instantchalcogenide alloys is reduced or eliminated. In one embodiment,formation of the device in its as-fabricated (virgin) state requires nomore than one step of setting the device and one step of resetting thedevice. In a preferred embodiment, formation of the device in itsas-fabricated (virgin) state requires no more than one step of settingthe device. In a more preferred embodiment, no formation of the devicein its as-fabricated (virgin) state is required.

In concert with the reduced or eliminated need for formation, the setresistance of the device stabilizes in a fewer number of cycles ofsetting and resetting such that the variation in the set resistance fromcycle-to-cycle is reduced. In one embodiment, the resistance of thefirst set state of the device differs from the resistance of the virginstate of the device by less than 50%. In a preferred embodiment, theresistance of the first set state of the device differs from theresistance of the virgin state of the device by less than 25%. Inanother preferred embodiment, the resistance of the second set state ofthe device differs from the resistance of the first set state of thedevice by less than 25%. In a more preferred embodiment, the resistanceof the first set state of the device differs from the resistance of thevirgin state of the device by less than 15%. In another more preferredembodiment, the resistance of the second set state of the device differsfrom the resistance of the first set state of the device by less than15%.

The results of this example support the conclusion that the need to forman as-fabricated chalcogenide memory diminishes and is eliminated as theGe and/or Te concentration is reduced. The data indicate that formationcharacteristics are improved when the atomic concentration of Ge is lessthan or equal to 20%. In a preferred embodiment, the atomicconcentration of Ge is less than or equal to 16%. In another preferredembodiment, the atomic concentration of Ge is less than or equal to 12%.The data indicate that improved formation characteristics are achievedwhen the atomic concentration of Te is less than or equal to 50%. In apreferred embodiment, the atomic concentration of Te is less than orequal to 40%. In another preferred embodiment, the atomic concentrationof Te is less than or equal to 30%. The data indicate that a preferredSb atomic concentration is at least 30%, a more preferred Sb atomicconcentration is at least 40% and another preferred Sb atomicconcentration is at least 50%.

Example 3

In this example, the speed advantage of the instant devices isdemonstrated. During operation of a memory device, it is necessary toprogram the device into and out of the set and reset states in mostapplications. Since establishment of the reset state can generally beaccomplished on shorter time scales than establishment of the set state,the programming speed of the device is controlled by the time requiredfor setting. (Typically, the time required to set (time-to-set) is afactor of 10 or more greater than the time to reset.) Since thetime-to-set is governed by the underlying crystallization process, it isdesirable to develop chalcogenide materials suitable for use in memorydevices that exhibit fast crystallization so that the set speed of thedevice can be shortened. The devices used in this example correspond tothose described in EXAMPLE 1 hereinabove. Devices included selectedchalcogenide compositions from those presented in EXAMPLE 1 aredescribed.

In this example, the time-to-set was measured by applying voltage pulsesto a device in its reset state and determining the minimum pulsefalltime required to transform the chalcogenide device to its set state.As described hereinabove, attainment of the set state from the resetstate entails providing energy to the chalcogenide material. When avoltage pulse is applied, the energy supplied to the chalcogenidematerial increases as the time of exposure of the device to the pulseincreases. The chalcogenide material accumulates the energy and respondsthrough an increase in its crystalline volume fraction until the setstate is achieved. The speed of operation of the device depends on theminimum time necessary to transform the device to its set state.

The time-to-set for devices containing several chalcogenide compositionswas measured. Each device was first reset by applying a 2.5 V pulsehaving a duration of 20 ns. A set pulse also having an amplitude of 2.5V was then applied. The set pulse had the following timecharacteristics: 10 ns risetime, 30 ns width, and variable falltime. Thefalltime was initially set at 199 ns and was systematically reduced todetermine the minimum falltime required to transform the device into itsset state. Upon conclusion of a set pulse with a particular falltime,the device resistance was measured to determine if the device was in itsset state. If the device was found to be in its set state, it was resetwith a reset pulse having an amplitude of 2.5 V and a duration of 20 nsand the experiment was repeated with a set pulse having a shorterfalltime. The procedure was repeated until the minimum falltime neededto establish the set state was determined. (Set pulses having a falltimeshorter than the minimum so-determined provide insufficient energy toset the device and lead to a device having a resistance that exceeds theset resistance.) The minimum falltime corresponds to a measure of thetime required to set the device and may be referred to herein as thetime-to-set the device.

Results from the time-to-set measurements are shown in FIG. 12 andsummarized in the following table, which shows the falltime determinedfor devices containing the active chalcogenide materials indicated.

Chalcogenide Composition of Device Time-to-Set (ns) Ge₂₅Sb₂₅Te₅₀ ~150Ge_(22.2)Sb_(22.2)Te_(55.5) ~150 Ge₂₀Sb₃₀Te₅₀ ~120Ge_(17.8)Sb_(37.8)Te_(44.4) ~60-75 Ge_(15.5)Sb_(45.5)Te₃₉ ~22-40Ge_(11.1)Sb_(61.1)Te_(27.8) ~25The results indicate that the time-to-set of the device decreases as theGe and/or Te composition of the active chalcogenide layer decreases. Thetime-to-set associated with the commonly employed Ge₂Sb₂Te₅(Ge_(22.2)Sb_(22.2)Te_(55.5)) material is much longer than thetime-to-set associated with any of the instant chalcogenide materials.The instant chalcogenide materials thus lead to faster operationalspeeds since a shorter time is needed to set the device.

In one embodiment, the Ge concentration of the chalcogenide material isless than or equal to 20%. In a preferred embodiment, the Geconcentration of the chalcogenide material is less than or equal to 18%.In a more preferred embodiment, the Ge concentration of the chalcogenidematerial is less than or equal to 16%. In another more preferredembodiment, the Ge concentration of the chalcogenide material is lessthan or equal to 13%.

In one embodiment, the Te concentration of the chalcogenide material isless than or equal to 50%. In a preferred embodiment, the Teconcentration of the chalcogenide material is less than or equal to 45%.In a more preferred embodiment, the Te concentration of the chalcogenidematerial is less than or equal to 40%. In another more preferredembodiment, the Te concentration of the chalcogenide material is lessthan or equal to 30%. The data indicate that a preferred Sb atomicconcentration is at least 30%, a more preferred Sb atomic concentrationis at least 45% and another more preferred Sb atomic concentration is atleast 60%.

In one embodiment, the time required to set a device including as anactive layer a chalcogenide material according to the instant inventionis less than or equal to 75% of the time required to set the same devicewhen Ge_(22.2)Sb_(22.2)Te_(55.5) is used as the active chalcogenidelayer in the device. In this embodiment, the device configuration,volume and shape of active chalcogenide material, and electrical signalused to set are the same when an instant chalcogenide alloy is used asthe active material as when Ge_(22.2)Sb_(22.2)Te_(55.5) is used as theactive chalcogenide material. In a preferred embodiment, the timerequired to set a device including as an active layer a chalcogenidematerial according to the instant invention is less than or equal to 50%of the time required to set the same device whenGe_(22.2)Sb_(22.2)Te_(55.5) is used as the active chalcogenide layer. Inthis embodiment, the device configuration, volume and shape of activechalcogenide material, and electrical signal used to set are the samewhen an instant chalcogenide alloy is used as the active material aswhen Ge_(22.2)Sb_(22.2)Te_(55.5) is used as the active chalcogenidematerial. In a more preferred embodiment, the time required to set adevice including as an active layer a chalcogenide material according tothe instant invention is less than or equal to 30% of the time requiredto set the same device when Ge_(22.2)Sb_(22.2)Te_(55.5) is used as theactive chalcogenide layer. In this embodiment, the device configuration,volume and shape of active chalcogenide material, and electrical signalused to set are the same when an instant chalcogenide alloy is used asthe active material as when Ge_(22.2)Sb_(22.2)Te_(55.5) is used as theactive chalcogenide material.

Example 4

In this example, the thermal stability characteristics of some of thememory devices described in EXAMPLE 1 hereinabove are described. Asdescribed hereinabove, elevation of temperature can lead to changes inthe relative proportions of crystalline and amorphous phases in a volumeof the active chalcogenide material, thus leading to an alteration ofthe memory state of a memory device and loss of information. Since atransformation of amorphous regions to a crystalline state can occur ata lower temperature than a transformation of crystalline regions to anamorphous state, thermal stability is best assessed in terms of acrystallization process.

In this example, we assess thermal stability in terms of the timerequired to transform a device from its reset state for several deviceshaving different compositions of the active chalcogenide layer. Thismeasure of thermal stability assesses the stability of informationstored as the reset state to thermally induced setting due to acrystallization process. All measurements described in this example wereperformed on devices requiring no further formation.

In the thermal stability experiments of this EXAMPLE, each device wasfirst reset, then heated to a particular temperature on a hot plate andfinally, the resistance of the device was measured as a function of timeat that temperature. The transition from the reset state to the setstate was detected as a decrease in the resistance of the device asdescribed hereinabove in connection with FIG. 1. In this EXAMPLE, thetime required to transform the device from its reset state to its setstate was selected to correspond to the time required for the resistanceof the device, beginning in the reset state, to decrease to less than 10kΩ. (For the purposes of this example, a resistance of less than 10 kΩwas selected to be sufficient to conclude that the device had beentransformed to its set state.) The procedure was repeated for eachdevice at several temperatures to determine the temperature dependenceof the time required to transform the device from its reset state to itsset state.

An Arrhenius plot of the transformation time as a function of (kT)⁻¹(where k is Boltzmann's constant and T is absolute temperature in K) wasprepared from the data. The thermal stability was assessed through alinear extrapolation of the transformation time from the timesrepresented in the data set to a time of 10 years and determining thetemperature associated with that time. This thermal stability metric isreferred to herein as the ten-year data retention temperature andcorresponds to the temperature at which data in the device can bemaintained for 10 years without loss. When the temperature of the deviceis elevated above the ten-year data retention temperature, loss ofinformation stored as the reset state occurs in less than 10 years andif the temperature of the device is reduced below the ten-year dataretention temperature, the information is retained for more than 10years.

The results of the thermal stability experiment of this EXAMPLE aresummarized below:

Device Chalcogenide Ten-year Data Retention Temperature (° C.)Ge_(11.1)Sb_(61.1)Te_(27.8) 95 Ge_(15.5)Sb_(45.5)Te_(38.9) 145Ge_(17.8)Sb_(37.8)Te_(44.4) 135 Ge_(22.2)Sb_(22.2)Te_(55.5) 115Ge₂₅Sb₂₅Te₅₀ 85

In one embodiment, the ten-year data retention temperature is at least120° C. In a preferred embodiment, the ten-year data retentiontemperature is at least 130° C. In a more preferred embodiment, theten-year data retention temperature is at least 140° C.

The thermal stability data show that the ten-year data retentiontemperature initially increases as the Ge atomic concentration isreduced below the amount present in the conventional Ge₂Sb₂Te₅ alloycomposition commonly used in current devices and then decreases. Thedata retention improves as the Ge atomic concentration is reduced to˜18% and then to ˜16%. At ˜11% Ge, however, the data retentioncharacteristics degrade and thermally induced setting of informationoccurs at lower temperatures. The data indicate that a preferred Geatomic concentration is in the range of 13%-19%, a more preferred Geatomic concentration is in the range of 14%-18%, and a most preferred Geatomic concentration is in the range of 15%-17%. The data indicate thata preferred Te atomic concentration is in the range of 27-56%, a morepreferred Te atomic concentration is in the range of 32-51%, and a mostpreferred Te atomic concentration is in the range of 37%-46%. The dataindicate that a preferred Sb atomic concentration is at least 30%, amore preferred Sb atomic concentration is at least 45% and a mostpreferred Sb atomic concentration is at least 60%.

Example 5

In this example, the reset current characteristics of some of the memorydevices described in EXAMPLE 1 hereinabove are described. This examplespecifically demonstrates differences in the reproducibility of thereset current for devices that include active chalcogenide materials ofdifferent compositions. More particularly, this example demonstratestrends in the reproducibility of the reset current with the atomicconcentration of different elements contained within the chalcogenidematerial.

The reset current described in this example is the current required totransform the device to its reset state. Illustrative resistance as afunction of current plots for selected devices were presented anddescribed in FIGS. 1-5 hereinabove. The reset currents presented in thisexample correspond to the reset current required to form the reset stateof the device after the device characteristics have stabilized and anytransient or formation effects associated with the devices have beenameliorated by an appropriate number of cycles of setting and resettingthe devices as described hereinabove.

The reset currents of several devices are summarized in FIG. 12. Theresults are presented in the form of reset current as a function of theelemental composition of the active chalcogenide material of the device.Reset currents are plotted separately as a function of the atomiccomposition of each element of the active chalcogenide material. Thereset current of each device is plotted separately as a function of theatomic compositions of Ge, Sb, and Te present in the active chalcogenidematerial of the device so that three points appear in FIG. 12 for eachdevice. The reset current for several different devices having each ofthe distinct chalcogenide compositions was measured and is presented inFIG. 12 to illustrate the reproducibility of reset current for differentdevices having the same chalcogenide composition.

In FIG. 12, reset current is plotted as a function of the atomicpercentages of Ge, Sb and Te in the active chalcogenide compositionusing diamond symbols, square symbols, and triangle symbols,respectively. Also included are three ovals that designate the preferredatomic percentage of each element within the active chalcogenidematerial. The range of preferred composition for each element in thecontext of this example is based on the consistency of the reset currentobserved over the range for several devices.

The left oval depicts the preferred range of Ge atomic composition andextends from about 11.5% to about 20%. In this range of Ge compositions,the reproducibility of the reset current from device-to-device is highas the reset currents of different devices that include Ge compositionswithin this range are similar and thus show consistent performance. Thespread of reset currents for compositions within the range depicted bythe oval is generally less than for compositions outside the rangedepicted by the oval. The spread in the reset current at an atomiccomposition of Ge of 25%, for example, is much greater than at atomiccompositions of Ge within the Ge oval.

The middle oval depicts the preferred range of Sb atomic composition andextends from about 19.5% to about 38%. In this range of Sb compositions,the reproducibility of the reset current from device-to-device is highas the reset currents of different devices that include Sb compositionswithin this range are similar and thus show consistent performance. Thespread of reset currents for compositions within the range depicted bythe oval is generally less than for compositions outside the rangedepicted by the oval. The spread in the reset current at an atomiccomposition of Sb of 30%, for example, is much lower than at atomiccompositions of Ge (e.g 45%) outside the Sb oval.

The right oval depicts the preferred range of Te atomic composition andextends from about 39% to about 57.5%. In this range of Te compositions,the reproducibility of the reset current from device-to-device is highas the reset currents of different devices that include Te compositionswithin this range are similar and thus show consistent performance. Thespread of reset currents for compositions within the range depicted bythe oval is generally less than for compositions outside the rangedepicted by the oval. The spread in the reset current at an atomiccomposition of Te of 30%, for example, is much greater than at atomiccompositions of Te within the Te oval.

Variations in the reset current provide a measure of the stability andconsistency of performance of different chalcogenide materials in atypical two-terminal device structure. Compositions that showreproducible and consistent reset currents over different devices areindicative of more stable intrinsic behavior of the chalcogenide. Thesecompositions may provide advantages in array structures containing alarge number of devices where consistency of performance across thearray of devices is desired.

The instant invention provides chalcogenide materials and devicescontaining same that provide benefits in terms of device performancefactors that include a reduction in the need for electrical deviceformation and/or faster operation by virtue of a shorter time-to-setand/or longer data retention times by virtue of improved thermalstability. While the optimal atomic concentrations may vary slightlydepending on the particular performance factor of interest, the instantchalcogenide materials generally include Ge and Sb where the atomicconcentration of Ge is less than or equal to 20% and the atomicconcentration of Sb is greater than or equal to 30%. In a preferredembodiment, the atomic concentration of Ge is less than or equal to 16%and the atomic concentration of Sb is greater than or equal to 40%. In amore preferred embodiment, the atomic concentration of Ge is less thanor equal to 12% and the atomic concentration of Sb is greater than orequal to 50%.

In other embodiments, the instant chalcogenide material includes Ge andSb as described above and further includes Te. In a preferredembodiment, the atomic concentration of Te is less than or equal to 50%and preferably between 20% and 50%. In another preferred embodiment, theatomic concentration of Te is less than or equal to 40% and preferablybetween 30% and 40%. In still another preferred embodiment, the atomicconcentration of Te is less than or equal to 30%.

Preferred chalcogenide compositions may differ depending on the propertyor combinations of properties of the chalcogenide material or devicecontaining same that one wishes to emphasize or design for. Relevantdevice properties include the speed, reset current, reset resistance,virgin resistance and holding voltage. In another embodiment of theinstant invention, suitable characteristics can be obtained when theatomic concentration of Ge is between 15% and 20% and the atomicconcentration of Te is between 39% and 42%.

The instant invention further includes embodiments having functionalequivalents to the illustrative embodiments described hereinabove. Asdescribed in several of the U.S. patents incorporated by referencehereinabove, chalcogenide materials generally include a chalcogenelement and one or more chemical or structural modifying elements. Thechalcogen element (e.g. Te, Se) is selected from column VI of theperiodic table and the modifying elements can be selected from columnIII (e.g. Ga, Al, In), column IV (e.g. Si, Ge, Sn), or column V (e.g. P,As, Sb) of the periodic table. The role of modifying elements includesproviding points of branching or crosslinking between chains comprisingthe chalcogen element. Column IV modifiers can function astetracoordinate modifiers that include two coordinate positions within achalcogenide chain and two coordination positions that permit branchingor crosslinking away from the chalcogenide chain. Column III and Vmodifiers can function as tricoordinate modifiers that include twocoordinate positions within a chalcogenide chain and one coordinateposition that permits branching or crosslinking away from thechalcogenide chain. Although the embodiments described hereinabove haveillustrated the features of the instant invention using chalcogenidematerials that include Ge, Sb, and/or Te, it is to be understood bythose of skill in the art that Ge may be substituted in whole or in partwith another column IV element (e.g. Si), Sb may be substituted in wholeor in part with another column V element (e.g. As), and Te may besubstituted in whole or in part with another column VI element (e.g.Se).

In addition to individual devices, the instant invention further extendsto arrays of devices. The instant chalcogenide materials and devices canbe integrated into arrays, including X-Y arrays, such as those describedin U.S. Pat. Nos. 5,694,146; 5,912,839; and 6,141,241; the disclosuresof which are hereby incorporated by reference. Chalcogenide devicearrays may be used for both memory and processing capabilities;including logic and parallel computing.

The foregoing discussion and description are not meant to be limitationsupon the practice of the present invention, but rather illustrativethereof. It is to be appreciated by persons of skill in the art thatnumerous equivalents of the illustrative embodiments disclosed hereinexist. It is the following claims, including all equivalents and obviousvariations thereof, in combination with the foregoing disclosure whichdefine the scope of the invention.

1. A method of operating a device comprising: forming a chalcogenidematerial; said chalcogenide material having an as-fabricated state, saidas-fabricated state having a virgin resistance; applying a first energyto said as-fabricated state of said chalcogenide material, said firstenergy transforming said chalcogenide material to a first set state,said first set state having a first resistance, said first resistancebeing between 75% and 125% of said virgin resistance.
 2. The method ofclaim 1, wherein said first resistance is between 85% and 115% of saidvirgin resistance.
 3. The method of claim 1, wherein said first energyis electrical energy.
 4. The method of claim 1, wherein said firstenergy increases the fractional crystallinity of said chalcogenidematerial.
 5. The method of claim 1, further comprising applying a secondenergy to said chalcogenide material, said second energy transformingsaid chalcogenide material from said first set state to a first resetstate.
 6. The method of claim 5, wherein said second energy decreasesthe fractional crystallinity of said chalcogenide material.
 7. Themethod of claim 5, wherein said second energy melts said chalcogenidematerial.
 8. The method of claim 5, further comprising applying a thirdenergy to said chalcogenide material, said third energy transformingsaid chalcogenide material from said first reset state to a second setstate, said second set state having a second resistance, said secondresistance being between 75% and 125% of said first resistance.
 9. Themethod of claim 8, wherein said second resistance is between 85% and115% of said first resistance.
 10. The method of claim 8, wherein saidsecond energy and said third energy are electrical energy.
 11. Themethod of claim 8, wherein the resistance of said first reset state isat least twice the resistance of said first set state.
 12. The method ofclaim 8, wherein the resistance of said first reset state is at least anorder of magnitude greater than the resistance of said first set state.13. The method of claim 8, wherein the resistance of said first resetstate is at least twice the resistance of said second set state.
 14. Themethod of claim 8, wherein the resistance of said first reset state isat least an order of magnitude greater than the resistance of saidsecond set state.
 15. The method of claim 8, wherein the time ofapplication of said third energy is less than or equal to 150 ns. 16.The method of claim 8, further comprising applying a fourth energy tosaid chalcogenide material, said fourth energy transforming saidchalcogenide material from said second set state to a second resetstate.
 17. The method of claim 16, further comprising applying a fifthenergy to said chalcogenide material, said fifth energy transformingsaid chalcogenide material from said second reset state to a third setstate, said third set state having a third resistance, said thirdresistance being between 85% and 115% of said second resistance.
 18. Themethod of claim 17, wherein said fourth energy and said fifth energy areelectrical energy.
 19. The method of claim 17, wherein the resistance ofsaid second reset state is at least twice the resistance of said secondset state.
 20. The method of claim 17, wherein the resistance of saidsecond reset state is at least twice the resistance of said third setstate.